CN105413412A - Cross-linkable intrinsically-porous polymer gas separation membrane and preparation method thereof - Google Patents

Cross-linkable intrinsically-porous polymer gas separation membrane and preparation method thereof Download PDF

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CN105413412A
CN105413412A CN201510742661.6A CN201510742661A CN105413412A CN 105413412 A CN105413412 A CN 105413412A CN 201510742661 A CN201510742661 A CN 201510742661A CN 105413412 A CN105413412 A CN 105413412A
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separation membrane
preparation
gas separation
chain
microporous polymer
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CN105413412B (en
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李南文
张淑芳
和树庆
王旭超
刘磊
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/02—Loose filtering material, e.g. loose fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D2053/221—Devices
    • B01D2053/223—Devices with hollow tubes
    • B01D2053/224—Devices with hollow tubes with hollow fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes

Abstract

It is a kind of cross-linking from tool microporous polymer gas separation membrane, it is characterised in that general structure is as follows: Wherein, 0 amp; amp; lt; m≤1. There is the present invention raw material to be easy to get, is easy to operate, mild condition, gas separation membrane good mechanical property and the high advantage of selectivity.

Description

Crosslinkable is from tool microporous polymer gas separation membrane and preparation method thereof
Technical field
The present invention relates to a kind of gas separation membrane and preparation method thereof, particularly relate to crosslinkable from tool microporous polymer (PIMs) gas separation membrane and preparation method thereof.
Background technology
2004, the people such as Budd synthesized rigidity, containing twist structured chain from tool microporous polymer PIM1-6, because its main chain can not freely rotate, therefore, it is possible to hinder the effective accumulation between strand well, film inside is impelled to form continuous print micropore, the membrane material obtained has good permeability and selective, presents certain superiority in gas separaion.
In recent years, by changing chain from the spirane structure of tool microporous polymer (PIMs) and carry out functionalization to it, improve the existing a large amount of report of work of gas separating property.Wherein, the introducing of more classical is exactly tetrazol group in backbone structure can improve selective (DuNY.etal.Nat.Mater., 2011, the 372-375) of gas separaion well.But, due to chain from the polymer of tool microporous polymer (PIMs) and most of functionalization only at common non-polar solven, as having good dissolubility in oxolane and chloroform equal solvent, and at polar solvent, as shown poor dissolubility in DMF, 1-METHYLPYRROLIDONE, therefore, deliquescent problem constrains its further modification in experimentation, especially in the application in spinning that moves towards the industrialization.
Meanwhile, under elevated pressure conditions, compressibility gas, as propylene/propane and carbon dioxide/methane, has certain plastication for this base polymer, thus causes the selective of its divided gas flow greatly to reduce.
Therefore, how chain is modified and functionalization further from tool microporous polymer (PIMs), improving the dissolubility of polymer in polar solvent, and improve the performance of its anti-plasticizing under elevated pressure conditions, is urgent problem in current research work.
Summary of the invention
The object of this invention is to provide one and have that raw material is easy to get, simple to operate, mild condition, gas separation membrane good mechanical property and selective high crosslinkable are from tool microporous polymer gas separation membrane and preparation method thereof.
The invention provides a kind of chain of functionalization from tool microporous polymer (PIMs), general structure is as follows:
Wherein, 0<m≤1.
R 1the structure of monomer is:
R 2monomer structure is:
Bromo chain provided by the invention comprises the steps: from the preparation method of tool microporous polymer (C) from tool microporous polymer (B) and Azide chain
Wherein, 0<m≤1.
(1) synthesis of polymer A: at N 2under stream protection, by R 1monomer, R 2monomer, K 2cO 3joining than the ratio of 1:1:2.5 ~ 3 in amount of substance is equipped with in 1-METHYLPYRROLIDONE (NMP) and toluene Mixed Solvent that volume ratio is 2 ~ 5:1, be placed in 140 DEG C ~ 160 DEG C constant temperature oil baths, after reaction 3 ~ 6h, the solution of thickness is poured in methyl alcohol at leisure, suction filtration, obtains jonquilleous fibrous polymer, then uses methyl alcohol, distilled water washing copolymer 3-5 time successively, lower 100 DEG C ~ 160 DEG C of vacuum condition is dried to constant weight, obtains yellow fluorescence product A;
(2) bromo chain is prepared from tool microporous polymer gas separation membrane: polymer A is dissolved in chlorobenzene the solution forming mass concentration 1 ~ 10%, magnetic agitation, after forming homogeneous phase solution, add the mixture of N-bromo-succinimide (NBS) and azodiisobutyronitrile (AIBN), wherein the ratio of amount of substance is polymer A: NBS:AIBN=1:0.2 ~ 2:0.02 ~ 0.2, in 100 ~ 150 DEG C of heating, react 3 ~ 5 hours, precipitate in methyl alcohol, and wash 3-5 time, filter, dry, obtain bromo chain from tool microporous polymer B;
The bromo chain of preparation is dissolved in chloroform from tool microporous polymer B, obtain the casting solution that concentration is 1-5wt%, after filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain bromo chain from tool microporous polymer gas separation membrane;
(3) Azide chain is prepared from tool microporous polymer gas separation membrane: the bromo chain of preparation in step (2) is dissolved in polar solvent from tool microporous polymer B the solution forming mass concentration 1 ~ 10%, magnetic agitation, add sodium azide after forming homogeneous phase solution, wherein bromo chain is from tool microporous polymer: NaN 3ratio=1:2 ~ 10 of amount of substance, add thermal response 12 ~ 24 hours, at methyl alcohol in 60 ~ 80 DEG C: the volume ratio of water is precipitate in the mixed solution of 1 ~ 5:1, and respectively with this mixed solution washing 3 ~ 5 times, filter, dry, obtain Azide chain from tool microporous polymer C;
The bromo chain of preparation is dissolved in chloroform from tool microporous polymer C, obtain the casting solution that concentration is 1-5wt%, after filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain Azide chain from tool microporous polymer gas separation membrane;
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 200 ~ 250 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 12 ~ 24h;
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 150 ~ 200 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 12 ~ 24h.
Polar solvent described in step 3 is 1-METHYLPYRROLIDONE (NMP), DMF (DMF) or DMA (DMAc).
The present invention compared with prior art tool has the following advantages:
1, raw material sources are extensive, low price.
2, the chain of functionalization is high from the synthesis efficiency of tool microporous polymer (PIMs), and reaction condition is gentle.
3, the bromo obtained and Azide chain, from selective higher for titanium dioxide carbon/nitrogen gas and oxygen/nitrogen of tool microporous polymer (PIMs), can meet the requirement of gas separaion practical application.
The chain of the bromo 4, obtained and Azide functionalization can be dissolved in polar solvent from tool microporous polymer (PIMs) well, is applied to industrialized prospect.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum of bromo of the present invention polymerization.
Fig. 2 is the structural formula of Azide polymer of the present invention.
Fig. 3 is the nucleus magnetic hydrogen spectrum of Azide of the present invention polymerization.
Detailed description of the invention
Further describe preparation method and the performance of the gas separation membrane that the present invention relates to below by way of example, but do not represent the restriction to this patent.
Embodiment 1
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), TFTPN (2.001g, 0.01mol) and K 2cO 3(3.45g, 0.025mol) be dissolved in 18mLN, in the mixed solvent of N-dimethylacetylamide (DMAc) and 9mL toluene, mechanical agitation, reacted at 150 DEG C after 5 hours, the solution of thickness is poured in methyl alcohol at leisure, suction filtration, obtains jonquilleous fibrous polymer, then uses methyl alcohol, distilled water washing copolymer 3-5 time successively, lower 120 ° of vacuum condition is dried to constant weight, obtains yellow fluorescence polymer P IM-CH 3, conversion ratio is 95%.
Its structural formula is as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 2.44g polymer P IM-CH 3be dissolved in 250mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 1.82gN-bromo-succinimide and 0.16g azodiisobutyronitrile, react at 150 DEG C after 5 hours, precipitate in methyl alcohol, after washing 5 times, after filtration, drying, obtain the polymer (bromo degree 100%) of bromo.Its structural formula is as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 3wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 374Barrer and 1686Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.3 and 28.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the brominated polymers obtained in step (2), get 6.5g and be dissolved in 650mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 6.5g Sodium azide, react at 80 DEG C after 24 hours, at methyl alcohol: the volume ratio of water is the precipitation of 5:1, after washing 5 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula is as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 5wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 380Barrer and 1840Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.2 and 26.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 200 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 24h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1500Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 150 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 24h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1100Barrer, but CO 2/ N 2selectively bring up to 27, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 2
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (11.052g, 0.03mol), TFTPN (6.003g, 0.03mol) and K 2cO 3(11.04g, 0.08mol) be dissolved in 56mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 11mL toluene, mechanical agitation, react at 160 DEG C after 5 hours, precipitate in methyl alcohol, after washing 4 times with methyl alcohol and distilled water successively, after filtration, drying, obtain polymer P IM-CH 3, conversion ratio is 93%.
Its structural formula is as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 7.3g polymer P IM-CH 3be dissolved in 150mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 1.6gN-bromo-succinimide and 0.15g azodiisobutyronitrile, react after 4 hours at 130 DEG C, precipitate in methyl alcohol, after washing 4 times, after filtration, drying, obtain the polymer (bromo degree 50%) of bromo.
Its structural formula (m=0.5) as follows:
Preparation brominated polymers A is dissolved in chloroform, obtains the casting solution that mass fraction is 1wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 725Barrer and 3250Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.6 and 20.3.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 5.67g and be dissolved in 57mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 1.8g Sodium azide, react at 70 DEG C after 12 hours, at methyl alcohol: the volume ratio of water is the precipitation of 4:1, after washing 4 times, after filtration, drying, obtain the polymer of Azide.Its structural formula (m=0.5) as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 430Barrer and 2050Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.4 and 21.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 250 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 12h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1430Barrer, but CO 2/ N 2selectively bring up to 30, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 200 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 12h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 952Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 3
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), TTSBI (6.808g, 0.02mol), TFTPN (6.003g, 0.03mol) and K 2cO 3(12.4g, 0.09mol) is dissolved in 55mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 14mL toluene, mechanical agitation, reacts after 5 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 4 times, after filtration, drying, obtain polymer CO-PIM-CH 3-1, conversion ratio is 93%.
Its structural formula (n=0.33) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.72g polymer CO-PIM-CH 3-1 is dissolved in 47mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 1.2gN-bromo-succinimide and 0.11g azodiisobutyronitrile, react at 150 DEG C after 5 hours, precipitate in methyl alcohol, after washing 5 times, after filtration, drying, obtain the polymer (bromo degree 33%) of bromo.Its structural formula (m=0.33) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 5wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 496Barrer and 3250Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.4 and 23.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 5.24g and be dissolved in 53mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 0.43g Sodium azide, react at 80 DEG C after 24 hours, at methyl alcohol: the volume ratio of water is the precipitation of 5:1, after washing 5 times, after filtration, drying, obtain the polymer of Azide.Its structural formula (m=0.33) as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 5wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 594Barrer and 3269Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.5 and 25.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 250 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 12h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1536Barrer, but CO 2/ N 2selectively bring up to 30, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 200 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 12h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 2450Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 4
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), TTSBI (3.404g, 0.01mol), TFTPN (4.002g, 0.02mol) and K 2cO 3(8.3g, 0.06mol) is dissolved in 37mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 19mL toluene, mechanical agitation, reacts after 3 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 4 times, after filtration, drying, obtain polymer CO-PIM-CH 3-1, conversion ratio is 93%.
Its structural formula (n=0.67) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.8g polymer CO-PIM-CH 3-1 is dissolved in 480mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 1.2gN-bromo-succinimide and 0.11g azodiisobutyronitrile, react at 150 DEG C after 3 hours, precipitate in methyl alcohol, after washing 3 times, after filtration, drying, obtain the polymer (bromo degree 67%) of bromo.
Its structural formula (m=0.67) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 5wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 693Barrer and 2658Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.3 and 20.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 5.9g and be dissolved in 60mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 4.4g Sodium azide, react at 60 DEG C after 24 hours, at methyl alcohol: the volume ratio of water is the precipitation of 1:1, after washing 4 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.67) as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 5%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 769Barrer and 3250Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.6 and 29.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 250 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 12h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 987Barrer, but CO 2/ N 2selectively bring up to 32, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 200 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 12h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 959Barrer, but CO 2/ N 2selectively bring up to 30, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 5
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), THDN (3.183g, 0.01mol), TFTPN (4.002g, 0.02mol) and K 2cO 3(6.9g, 0.054mol) is dissolved in 30mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 10mL toluene, mechanical agitation, reacts after 3 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 4 times, after filtration, drying, obtain polymer CO-PIM-CH 3-2, conversion ratio is 95%.
Its structural formula (n=0.5) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.6g polymer CO-PIM-CH 3-2 are dissolved in 200mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 1.78gN-bromo-succinimide and 0.17g azodiisobutyronitrile, react at 135 DEG C after 4 hours, precipitate in methyl alcohol, after washing 4 times, after filtration, drying, obtain the polymer (bromo degree 50%) of bromo.
Its structural formula (m=0.5) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 798Barrer and 2540Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.1 and 21.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 5.4g and be dissolved in 250mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 2.6g Sodium azide, react at 70 DEG C after 20 hours, at methyl alcohol: the volume ratio of water is the precipitation of 4:1, after washing 4 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.5) as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 3%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 958Barrer and 1750Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.9 and 25.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1350Barrer, but CO 2/ N 2selectively bring up to 30, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 985Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 6
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (7.368g, 0.02mol), THDN (3.183g, 0.01mol), TFTPN (6.003g, 0.03mol) and K 2cO 3(10.4g, 0.075mol) is dissolved in 55mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 28mL toluene, mechanical agitation, reacts after 6 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 4 times, after filtration, drying, obtain polymer CO-PIM-CH 3-2, conversion ratio is 95%.
Its structural formula (n=0.67) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.6g polymer CO-PIM-CH 3-2 are dissolved in 460mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 2.35gN-bromo-succinimide and 0.22g azodiisobutyronitrile, react at 150 DEG C after 4 hours, precipitate in methyl alcohol, after washing 5 times, after filtration, drying, obtain the polymer (bromo degree 67%) of bromo.
Its structural formula (m=0.67) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 596Barrer and 2658Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.5 and 29.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 5.97g and be dissolved in 597mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 0.86g Sodium azide, react at 60 DEG C after 12 hours, at methyl alcohol: the volume ratio of water is the precipitation of 3:1, after washing 3 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.67) as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 3wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 592Barrer and 1952Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.4 and 29.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1352Barrer, but CO 2/ N 2selectively bring up to 30, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 961Barrer, but CO 2/ N 2selectively bring up to 32, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 7
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), SFB (3.804g, 0.01mol), TFTPN (4.002g, 0.02mol) and K 2cO 3(6.9g, 0.05mol) is dissolved in 30mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 10mL toluene, mechanical agitation, reacts after 3 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 4 times, after filtration, drying, obtain polymer CO-PIM-CH 3-3, conversion ratio is 94%.
Its structural formula (n=0.5) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.9g polymer CO-PIM-CH 3-3 are dissolved in 50mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 1.78gN-bromo-succinimide and 0.164g azodiisobutyronitrile, react at 135 DEG C after 3 hours, precipitate in methyl alcohol, after washing 4 times, after filtration, drying, obtain the polymer (bromo degree 50%) of bromo.
Its structural formula (m=0.5) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 5%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 596Barrer and 3302Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.2 and 27.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 4.1g and be dissolved in 41mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 3.25g Sodium azide, react at 60 DEG C after 12 hours, at methyl alcohol: the volume ratio of water is the precipitation of 1:1, after washing 4 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.5) as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 5%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 524Barrer and 2150Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.3 and 27.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1362Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1059Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 8
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), SFB (7.608g, 0.02mol), TFTPN (6.003g, 0.03mol) and K 2cO 3(7.5g, 0.054mol) is dissolved in 58mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 29mL toluene, mechanical agitation, reacts after 3 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 3 times, after filtration, drying, obtain polymer CO-PIM-CH 3-3, conversion ratio is 94%.
Its structural formula (n=0.33) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.97g polymer CO-PIM-CH 3-3 are dissolved in 50mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 0.17gN-bromo-succinimide and 0.11g azodiisobutyronitrile, react at 100 DEG C after 3 hours, precipitate in methyl alcohol, after washing 4 times, after filtration, drying, obtain the polymer (bromo degree 33%) of bromo.
Its structural formula (m=0.33) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 5wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 596Barrer and 3330Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.2 and 27.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 5.75g and be dissolved in 60mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 2.15g Sodium azide, react at 60 DEG C after 12 hours, at methyl alcohol: the volume ratio of water is the precipitation of 1:1, after washing 4 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.33) as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 5%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 459Barrer and 1800Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.3 and 27.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1960Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1056Barrer, but CO 2/ N 2selectively bring up to 28, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 9
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), EA (2.343g, 0.01mol), TFTPN (4.002g, 0.02mol) and K 2cO 3(6.9g, 0.05mol) is dissolved in 30mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 10mL toluene, mechanical agitation, reacts after 3 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 4 times, after filtration, drying, obtain polymer CO-PIM-CH 3-4, conversion ratio is 93%.
Its structural formula (n=0.5) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.2g polymer CO-PIM-CH 3-4 are dissolved in 42mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 1.78gN-bromo-succinimide and 0.164g azodiisobutyronitrile, react at 100 DEG C after 3 hours, precipitate in methyl alcohol, after washing 4 times, after filtration, drying, obtain the polymer (bromo degree 50%) of bromo.
Its structural formula (m=0.5) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 5%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 524Barrer and 2350Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.8 and 28.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 3.4g and be dissolved in 34mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 3.3g Sodium azide, react at 60 DEG C after 12 hours, at methyl alcohol: the volume ratio of water is the precipitation of 1:1, after washing 4 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.5) as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 5%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 550Barrer and 1950Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.7 and 29.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1523Barrer, but CO 2/ N 2selectively bring up to 30, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1052Barrer, but CO 2/ N 2selectively bring up to 30, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 10
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), EA (4.686g, 0.02mol), TFTPN (6.003g, 0.02mol) and K 2cO 3(10.4g, 0.075mol) is dissolved in 48mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 24mL toluene, mechanical agitation, reacts after 3 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 3 times, after filtration, drying, obtain polymer CO-PIM-CH 3-4, conversion ratio is 93%.
Its structural formula (n=0.33) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.6g polymer CO-PIM-CH 3-4 are dissolved in 46mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 0.19gN-bromo-succinimide and 0.12g azodiisobutyronitrile, react at 100 DEG C after 3 hours, precipitate in methyl alcohol, after washing 3 times, after filtration, drying, obtain the polymer (bromo degree 33%) of bromo.
Its structural formula (m=0.33) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 3wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 535Barrer and 3253Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.3 and 25.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 4.95g and be dissolved in 50mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 2.14g Sodium azide, react at 60 DEG C after 12 hours, at methyl alcohol: the volume ratio of water is the precipitation of 3:1, after washing 3 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.33) as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 5%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 552Barrer and 1850Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.2 and 29.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1200Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1050Barrer, but CO 2/ N 2selectively bring up to 30, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 11
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), Trip (3.183g, 0.01mol), TFTPN (4.002g, 0.02mol) and K 2cO 3(6.9g, 0.05mol) is dissolved in 30mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 10mL toluene, mechanical agitation, reacts after 3 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 4 times, after filtration, drying, obtain polymer CO-PIM-CH 3-5, conversion ratio is 93%.
Its structural formula (n=0.5) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.6g polymer CO-PIM-CH 3-5 are dissolved in 47mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 1.78gN-bromo-succinimide and 0.164g azodiisobutyronitrile, react at 100 DEG C after 3 hours, precipitate in methyl alcohol, after washing 4 times, after filtration, drying, obtain the polymer (bromo degree 50%) of bromo.
Its structural formula (m=0.5) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 5%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 523Barrer and 5203Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.2 and 24.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 3.8g and be dissolved in 50mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 3.25g Sodium azide, react at 60 DEG C after 12 hours, at methyl alcohol: the volume ratio of water is the precipitation of 1:1, after washing 4 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.5) as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 5%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 617Barrer and 2568Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.0 and 23.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1051Barrer, but CO 2/ N 2selectively bring up to 27, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1204Barrer, but CO 2/ N 2selectively bring up to 27, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 12
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), Trip (6.366g, 0.02mol), TFTPN (6.003g, 0.03mol) and K 2cO 3(10.4g, 0.075mol) is dissolved in 54mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 27mL toluene, mechanical agitation, reacts after 3 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 3 times, after filtration, drying, obtain polymer CO-PIM-CH 3-5, conversion ratio is 93%.
Its structural formula (n=0.33) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.8g polymer CO-PIM-CH 3-5 are dissolved in 48mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 0.19gN-bromo-succinimide and 0.11g azodiisobutyronitrile, react at 100 DEG C after 3 hours, precipitate in methyl alcohol, after washing 3 times, after filtration, drying, obtain the polymer (bromo degree 33%) of bromo.
Its structural formula (m=0.33) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 3wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 325Barrer and 2500Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.1 and 23.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 5.3g and be dissolved in 53mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 2.16g Sodium azide, react at 60 DEG C after 12 hours, at methyl alcohol: the volume ratio of water is the precipitation of 3:1, after washing 4 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.33) as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 3wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 615Barrer and 3354Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.2 and 25.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1510Barrer, but CO 2/ N 2selectively bring up to 26, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 963Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 13
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (7.368g, 0.02mol), Trip (3.183g, 0.01mol), TFTPN (6.003g, 0.03mol) and K 2cO 3(12.4g, 0.09mol) is dissolved in 56mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 28mL toluene, mechanical agitation, reacts after 6 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 5 times, after filtration, drying, obtain polymer CO-PIM-CH 3-5, conversion ratio is 93%.
Its structural formula (n=0.67) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.8g polymer CO-PIM-CH 3-5 are dissolved in 480mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 0.19gN-bromo-succinimide and 0.13g azodiisobutyronitrile, react at 100 DEG C after 3 hours, precipitate in methyl alcohol, after washing 4 times, after filtration, drying, obtain the polymer (bromo degree 67%) of bromo.
Its structural formula (m=0.67) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 615Barrer and 5400Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.3 and 24.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 5.8g and be dissolved in 50mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 2.42g Sodium azide, react at 80 DEG C after 24 hours, at methyl alcohol: the volume ratio of water is the precipitation of 5:1, after washing 5 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.67) as follows:
Azide dissolution of polymer will be prepared in chloroform, obtain the casting solution that mass fraction is 5%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 596Barrer and 3526Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.0 and 23.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1250Barrer, but CO 2/ N 2selectively bring up to 28, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1023Barrer, but CO 2/ N 2selectively bring up to 28, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 14
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), TTSBI (3.404g, 0.01mol), DFBP (6.682g, 0.02mol) and K 2cO 3(6.9g, 0.05mol) is dissolved in 30mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 10mL toluene, mechanical agitation, reacts after 3 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 4 times, after filtration, drying, obtain polymer CO-PIM-CH 3-6, conversion ratio is 91%.
Its structural formula (n=0.5) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.6g polymer CO-PIM-CH 3-5 are dissolved in 47mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 1.78gN-bromo-succinimide and 0.164g azodiisobutyronitrile, react at 100 DEG C after 3 hours, precipitate in methyl alcohol, after washing 4 times, after filtration, drying, obtain the polymer (bromo degree 50%) of bromo.
Its structural formula (m=0.5) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 615Barrer and 5400Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.3 and 22
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 3.8g and be dissolved in 50mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 3.25g Sodium azide, react at 60 DEG C after 12 hours, at methyl alcohol: the volume ratio of water is the precipitation of 1:1, after washing 4 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.5) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 615Barrer and 1852Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.3 and 24
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1200Barrer, but CO 2/ N 2selectively bring up to 30, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1050Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 15
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), TTSBI (6.808g, 0.02mol), DFBP (20.046g, 0.03mol) and K 2cO 3(7.5g, 0.054mol) is dissolved in 102mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 51mL toluene, mechanical agitation, reacts after 3 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 3 times, after filtration, drying, obtain polymer CO-PIM-CH 3-6, conversion ratio is 91%.
Its structural formula (n=0.33) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 6.06g polymer CO-PIM-CH 3-5 are dissolved in 61mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 0.20gN-bromo-succinimide and 0.12g azodiisobutyronitrile, react at 100 DEG C after 3 hours, precipitate in methyl alcohol, after washing 4 times, after filtration, drying, obtain the polymer (bromo degree 33%) of bromo.
Its structural formula (m=0.33) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 615Barrer and 5236Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.3 and 21
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 6.33g and be dissolved in 65mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 2.26g Sodium azide, react at 60 DEG C after 12 hours, at methyl alcohol: the volume ratio of water is the precipitation of 3:1, after washing 3 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.33) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 615Barrer and 1650Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.3 and 23
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 4820Barrer, but CO 2/ N 2selectively bring up to 28, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1053Barrer, but CO 2/ N 2selectively bring up to 27, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 16
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (7.368g, 0.02mol), TTSBI (3.404g, 0.01mol), DFBP (20.046g, 0.03mol) and K 2cO 3(12.4g, 0.09mol) is dissolved in 103mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 52mL toluene, mechanical agitation, reacts after 6 hours at 160 DEG C, precipitates in a large amount of methyl alcohol, after washing 5 times, after filtration, drying, obtain polymer CO-PIM-CH 3-6, conversion ratio is 91%.
Its structural formula (n=0.67) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 6.33g polymer CO-PIM-CH 3-5 are dissolved in 630mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 2.4gN-bromo-succinimide and 0.25g azodiisobutyronitrile, react at 150 DEG C after 3 hours, precipitate in methyl alcohol, after washing 5 times, after filtration, drying, obtain the polymer (bromo degree 67%) of bromo.
Its structural formula (m=0.67) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 615Barrer and 3296Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.3 and 24.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 7.2g and be dissolved in 720mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 0.93g Sodium azide, react at 80 DEG C after 24 hours, at methyl alcohol: the volume ratio of water is the precipitation of 5:1, after washing 5 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.67) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 613Barrer and 956Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.9 and 21.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1032Barrer, but CO 2/ N 2selectively bring up to 30, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1030Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 17
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), TTSBI (3.404g, 0.01mol), DFBZPN (7.242g, 0.02mol) and K 2cO 3(6.9g, 0.05mol) is dissolved in 30mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 10mL toluene, mechanical agitation, reacts after 3 hours at 160 DEG C, precipitates in methyl alcohol, after washing 4 times, after filtration, drying, obtain polymer CO-PIM-CH 3-7, conversion ratio is 94%.
Its structural formula (n=0.5) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 4.6g polymer CO-PIM-CH 3-5 are dissolved in 47mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 1.78gN-bromo-succinimide and 0.164g azodiisobutyronitrile, react at 100 DEG C after 3 hours, precipitate in methyl alcohol, after washing 4 times, after filtration, drying, obtain the polymer (bromo degree 50%) of bromo.
Its structural formula (m=0.5) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 652Barrer and 4693Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.8 and 23.
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 3.8g and be dissolved in 50mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 3.25g Sodium azide, react at 60 DEG C after 12 hours, at methyl alcohol: the volume ratio of water is the precipitation of 1:1, after washing 4 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.5) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 275Barrer and 2403Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.2 and 24.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1263Barrer, but CO 2/ N 2selectively bring up to 30, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1030Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 18
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (3.684g, 0.01mol), TTSBI (6.808g, 0.02mol), DFBZPN (10.863g, 0.03mol) and K 2cO 3(7.46g, 0.054mol) is dissolved in 72mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 36mL toluene, mechanical agitation, reacts after 3 hours at 160 DEG C, precipitates in methyl alcohol, after washing 4 times, after filtration, drying, obtain polymer CO-PIM-CH 3-7, conversion ratio is 94%.
Its structural formula (n=0.33) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 6.33g polymer CO-PIM-CH 3-5 are dissolved in 63mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 0.21gN-bromo-succinimide and 0.11g azodiisobutyronitrile, react at 100 DEG C after 3 hours, precipitate in methyl alcohol, after washing 4 times, after filtration, drying, obtain the polymer (bromo degree 33%) of bromo.
Its structural formula (m=0.33) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 415Barrer and 5200Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.9 and 24
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 6.8g and be dissolved in 70mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 2.24g Sodium azide, react at 60 DEG C after 12 hours, at methyl alcohol: the volume ratio of water is the precipitation of 3:1, after washing 4 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.33) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 239Barrer and 1950Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 5.1 and 24.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1052Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 965Barrer, but CO 2/ N 2selectively bring up to 27, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
Embodiment 19
(1) synthesis of polymer: under nitrogen atmosphere protection, by monomer CH in there-necked flask 3-TTSBI (7.368g, 0.02mol), TTSBI (3.404g, 0.01mol), DFBZPN (10.863g, 0.02mol) and K 2cO 3(12.4g, 0.09mol) is dissolved in 72mLN, in the mixed solvent of N-dimethylacetylamide (DMAC) and 36mL toluene, mechanical agitation, reacts after 6 hours at 160 DEG C, precipitates in methyl alcohol, after washing 5 times, after filtration, drying, obtain polymer CO-PIM-CH 3-7, conversion ratio is 94%.
Its structural formula (n=0.67) as follows:
(2) bromo chain is from the preparation of tool microporous polymer membranes: by 6.4g polymer CO-PIM-CH 3-5 are dissolved in 640mL chlorobenzene, magnetic agitation, after forming homogeneous phase solution, add 2.35gN-bromo-succinimide and 0.22g azodiisobutyronitrile, react at 150 DEG C after 4 hours, precipitate in methyl alcohol, after washing 5 times, after filtration, drying, obtain the polymer (bromo degree 67%) of bromo.
Its structural formula (m=0.67) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 326Barrer and 5210Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.3 and 24
(3) Azide chain is from the preparation of tool microporous polymer membranes: by the polymer of bromo obtained in step 2, get 7.5g and be dissolved in 750mLN, in dinethylformamide, magnetic agitation, after forming homogeneous phase solution, adds 0.92g Sodium azide, react at 80 DEG C after 24 hours, at methyl alcohol: the volume ratio of water is the precipitation of 3:1, after washing 4 times, after filtration, drying, obtain the polymer of Azide.
Its structural formula (m=0.67) as follows:
Preparation brominated polymers is dissolved in chloroform, obtains the casting solution that mass fraction is 4wt%.After filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain the film that thickness is 60 ± 5 microns.At 100 psi, this gas separation membrane is to O 2and CO 2infiltration coefficient be respectively 230Barrer and 1860Barrer, O 2/ N 2and CO 2/ N 2permselective property be respectively 4.9 and 24.
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 225 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 1210Barrer, but CO 2/ N 2selectively bring up to 29, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 175 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 18h.When given gas pressure is increased to 700psi gradually by 100psi, uncrosslinked polymer film is to CO 2infiltration coefficient sharply rises at 500-700psi, shows CO 2certain plastication is had to this gas separation membrane; Gas separation membrane after crosslinked is to CO 2infiltration coefficient drops to 896Barrer, but CO 2/ N 2selectively bring up to 27, and do not occur plastifying phenomenon, illustrates crosslinked after gas separation membrane material maintenance is high-throughout while, there is good anti-plasticizing capacity.

Claims (5)

1. crosslinkable is from a tool microporous polymer gas separation membrane, it is characterized in that general structure is as follows:
Wherein, 0<m≤1.
2. a kind of crosslinkable as claimed in claim 1 is from tool microporous polymer gas separation membrane, it is characterized in that described R 1monomer structure is:
。
3. a kind of crosslinkable as claimed in claim 1 is from tool microporous polymer gas separation membrane, it is characterized in that described R 2monomer structure is:
。
4. a kind of crosslinkable as described in any one of claim 1-3, from the preparation method of tool microporous polymer gas separation membrane, is characterized in that comprising the steps:
(1) synthesis of polymer A: at N 2under stream protection, by R 1monomer, R 2monomer, K 2cO 3joining than the ratio of 1:1:2.5 ~ 3 in amount of substance is equipped with in 1-METHYLPYRROLIDONE and toluene Mixed Solvent that volume ratio is 2 ~ 5:1, be placed in 140 DEG C ~ 160 DEG C constant temperature oil baths, after reaction 3 ~ 6h, the solution of thickness is poured in methyl alcohol at leisure, suction filtration, obtains jonquilleous fibrous polymer, then uses methyl alcohol, distilled water washing copolymer 3-5 time successively, lower 100 DEG C ~ 160 DEG C of vacuum condition is dried to constant weight, obtains yellow fluorescence product A;
(2) bromo chain is prepared from tool microporous polymer gas separation membrane: polymer A is dissolved in chlorobenzene the solution forming mass concentration 1 ~ 10%, magnetic agitation, after forming homogeneous phase solution, add the mixture of N-bromo-succinimide and azodiisobutyronitrile, wherein the ratio of amount of substance is polymer A: NBS:AIBN=1:0.2 ~ 2:0.02 ~ 0.2, in 100 ~ 150 DEG C of heating, react 3 ~ 5 hours, precipitate in methyl alcohol, and wash 3-5 time, filter, dry, obtain bromo chain from tool microporous polymer B;
The bromo chain of preparation is dissolved in chloroform from tool microporous polymer B, obtain the casting solution that concentration is 1-5wt%, after filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain bromo chain from tool microporous polymer gas separation membrane;
(3) Azide chain is prepared from tool microporous polymer gas separation membrane: the bromo chain of preparation in step (2) is dissolved in polar solvent from tool microporous polymer B the solution forming mass concentration 1 ~ 10%, magnetic agitation, add sodium azide after forming homogeneous phase solution, wherein bromo chain is from tool microporous polymer: NaN 3ratio=1:2 ~ 10 of amount of substance, add thermal response 12 ~ 24 hours, at methyl alcohol in 60 ~ 80 DEG C: the volume ratio of water is precipitate in the mixed solution of 1 ~ 5:1, and respectively with this mixed solution washing 3 ~ 5 times, filter, dry, obtain Azide chain from tool microporous polymer C;
The bromo chain of preparation is dissolved in chloroform from tool microporous polymer C, obtain the casting solution that concentration is 1-5wt%, after filtration, casting solution is poured in clean horizontal glass pond, and at room temperature solvent flashing, obtain Azide chain from tool microporous polymer gas separation membrane;
(4) crosslinked bromo chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the bromo chain of preparation in step 2 is placed in 200 ~ 250 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 12 ~ 24h;
(5) crosslinked Azide chain is from the preparation of tool microporous polymer membranes: under argon gas condition, the Azide chain of preparation in step 3 is placed in 150 ~ 200 DEG C from tool microporous polymer membranes and heat-treats, crosslinked 12 ~ 24h.
5. a kind of crosslinkable as described in any one of claim 1-3 is from the preparation method of tool microporous polymer gas separation membrane, it is characterized in that the polar solvent described in step (3) is 1-METHYLPYRROLIDONE, N, dinethylformamide or DMA.
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KR101756345B1 (en) 2016-10-26 2017-07-11 한국과학기술연구원 Novel poly(arylene ether)s-based copolymer for electrode binder of fuel cell, membrane electrode assembly comprising the same and preparation method thereof
CN107652428A (en) * 2017-09-28 2018-02-02 厦门大学 A kind of micropore high-molecular copolymer membrane material of tool certainly and preparation method thereof
CN107774140A (en) * 2017-12-04 2018-03-09 中国石油大学(华东) A kind of preparation of door assembly with hinge and glass in right hand and left structure PIMs films and the application of gas separation field
CN109248567A (en) * 2018-08-31 2019-01-22 浙江工业大学 A kind of PIMs superthin layer composite hollow fiber membrane and preparation and application
CN110385114A (en) * 2019-06-27 2019-10-29 浙江工业大学 Compound derivative multifunctional C molecular sieve of metal-organic framework materials/autohemagglutination microporous polymer and the preparation method and application thereof
CN110461451A (en) * 2017-04-06 2019-11-15 陶氏环球技术有限责任公司 The thin-film composite membrane of TROGER alkali polymer including crosslinking
CN110508102A (en) * 2019-09-03 2019-11-29 长春工业大学 Poly- virtue fluorenes ether ketone Am-PAFEK and PIM-1 gas separation hybrid films and preparation method thereof
CN110787663A (en) * 2019-11-15 2020-02-14 中南大学 High permeability polymer composite membrane for gas separation and method of making the same
CN113024799A (en) * 2021-03-01 2021-06-25 山东大学 Application of soluble polymer with micropores in iodine vapor detection
CN114177744A (en) * 2022-02-17 2022-03-15 中国气象科学研究院 Trapezoidal polymer with micropores for gas separation, membrane and application
CN115155344A (en) * 2022-07-15 2022-10-11 大连理工大学 Preparation method of ester cross-linking modified microporous polymer gas separation membrane

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KR101756345B1 (en) 2016-10-26 2017-07-11 한국과학기술연구원 Novel poly(arylene ether)s-based copolymer for electrode binder of fuel cell, membrane electrode assembly comprising the same and preparation method thereof
KR101756343B1 (en) 2016-10-26 2017-07-11 한국과학기술연구원 Novel poly(arylene ether)s-based copolymer for electrode binder of fuel cell, membrane electrode assembly comprising the same and preparation method thereof
CN110461451A (en) * 2017-04-06 2019-11-15 陶氏环球技术有限责任公司 The thin-film composite membrane of TROGER alkali polymer including crosslinking
CN107652428A (en) * 2017-09-28 2018-02-02 厦门大学 A kind of micropore high-molecular copolymer membrane material of tool certainly and preparation method thereof
CN107774140B (en) * 2017-12-04 2020-12-01 中国石油大学(华东) Preparation of PIMs (particle implanted membranes) with hinge structure and application of PIMs in field of gas separation
CN107774140A (en) * 2017-12-04 2018-03-09 中国石油大学(华东) A kind of preparation of door assembly with hinge and glass in right hand and left structure PIMs films and the application of gas separation field
CN109248567A (en) * 2018-08-31 2019-01-22 浙江工业大学 A kind of PIMs superthin layer composite hollow fiber membrane and preparation and application
CN109248567B (en) * 2018-08-31 2021-07-27 浙江工业大学 PIMs ultrathin layer composite hollow fiber membrane and preparation and application thereof
CN110385114B (en) * 2019-06-27 2021-10-15 浙江工业大学 Metal organic framework material/self-polymerization microporous polymer composite derivative multifunctional carbon molecular sieve and preparation method and application thereof
CN110385114A (en) * 2019-06-27 2019-10-29 浙江工业大学 Compound derivative multifunctional C molecular sieve of metal-organic framework materials/autohemagglutination microporous polymer and the preparation method and application thereof
CN110508102A (en) * 2019-09-03 2019-11-29 长春工业大学 Poly- virtue fluorenes ether ketone Am-PAFEK and PIM-1 gas separation hybrid films and preparation method thereof
CN110787663A (en) * 2019-11-15 2020-02-14 中南大学 High permeability polymer composite membrane for gas separation and method of making the same
CN113024799A (en) * 2021-03-01 2021-06-25 山东大学 Application of soluble polymer with micropores in iodine vapor detection
CN114177744A (en) * 2022-02-17 2022-03-15 中国气象科学研究院 Trapezoidal polymer with micropores for gas separation, membrane and application
CN114177744B (en) * 2022-02-17 2022-04-15 中国气象科学研究院 Trapezoidal polymer with micropores for gas separation, membrane and application
CN115155344A (en) * 2022-07-15 2022-10-11 大连理工大学 Preparation method of ester cross-linking modified microporous polymer gas separation membrane
CN115155344B (en) * 2022-07-15 2023-09-22 大连理工大学 Preparation method of ester crosslinking modified microporous polymer gas separation membrane

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